Mixed-valence state of symmetric diruthenium complexes: synthesis, characterization, and electron transfer investigation

Complexes of the type {[(pyS)Ru(NH3)(4)](2)-mu-L}(n), where pyS = 4-mercaptopyridine, L = 4,4'-dithiodipyridine (pySSpy), pyrazine (pz) and 1,4-dicyanobenzene (DCB), and n = +4 and +5 for fully reduced and mixed-valence complexes, respectively, were synthesized and characterized. Electrochemical data showed that there is electron communication between the metal centers with comproportionation constants of 33.2, 1.30 x 10(8) and 5.56 x 10(5) for L = pySSpy, pz and DCB, respectively. It was also observed that the electronic coupling between the metal centers is affected by the p-back-bonding interaction toward the pyS ligand. Raman spectroscopy showed a dependence of the intensity of the vibrational modes on the exciting radiations giving support to the assignments of the electronic transitions. The degree of electron communication between the metal centers through the bridging ligands suggests that these systems can be molecular wire materials.

On the optical properties of copper nanocubes as a function of the edge length as modeled by the discrete dipole approximation

This Letter reports an investigation on the optical properties of copper nanocubes as a function of size as modeled by the discrete dipole approximation. In the far-field, our results showed that the extinction resonances shifted from 595 to 670 nm as the size increased from 20 to 100 nm. Also, the highest optical efficiencies for absorption and scattering were obtained for nanocubes that were 60 and 100 nm in size, respectively. In the near-field, the electric-field amplitudes were investigated considering 514, 633 and 785 nm as the excitation wavelengths. The E-fields increased with size, being the highest at 633 nm. (c) 2012 Elsevier B.V. All rights reserved.

Confocal microscopy applied to the study of single entity fluorescence and light scattering

A sample scanning confocal optical microscope (SCOM) was designed and constructed in order to perform local measurements of fluorescence, light scattering and Raman scattering. This instrument allows to measure time resolved fluorescence, Raman scattering and light scattering from the same diffraction limited spot. Fluorescence from single molecules and light scattering from metallic nanoparticles can be studied. First, the electric field distribution in the focus of the SCOM was modelled. This enables the design of illumination modes for different purposes, such as the determination of the three-dimensional orientation of single chromophores. Second, a method for the calculation of the de-excitation rates of a chromophore was presented. This permits to compare different detection schemes and experimental geometries in order to optimize the collection of fluorescence photons. Both methods were combined to calculate the SCOM fluorescence signal of a chromophore in a general layered system. The fluorescence excitation and emission of single molecules through a thin gold film was investigated experimentally and modelled. It was demonstrated that, due to the mediation of surface plasmons, single molecule fluorescence near a thin gold film can be excited and detected with an epi-illumination scheme through the film. Single molecule fluorescence as close as 15nm to the gold film was studied in this manner. The fluorescence dynamics (fluorescence blinking and excited state lifetime) of single molecules was studied in the presence and in the absence of a nearby gold film in order to investigate the influence of the metal on the electronic transition rates. The trace-histogram and the autocorrelation methods for the analysis of single molecule fluorescence blinking were presented and compared via the analysis of Monte-Carlo simulated data. The nearby gold influences the total decay rate in agreement to theory. The gold presence produced no influence on the ISC rate from the excited state to the triplet but increased by a factor of 2 the transition rate from the triplet to the singlet ground state. The photoluminescence blinking of Zn0.42Cd0.58Se QDs on glass and ITO substrates was investigated experimentally as a function of the excitation power (P) and modelled via Monte-Carlo simulations. At low P, it was observed that the probability of a certain on- or off-time follows a negative power-law with exponent near to 1.6. As P increased, the on-time fraction reduced on both substrates whereas the off-times did not change. A weak residual memory effect between consecutive on-times and consecutive off-times was observed but not between an on-time and the adjacent off-time. All of this suggests the presence of two independent mechanisms governing the lifetimes of the on- and off-states. The simulated data showed Poisson-distributed off- and on-intensities, demonstrating that the observed non-Poissonian on-intensity distribution of the QDs is not a product of the underlying power-law probability and that the blinking of QDs occurs between a non-emitting off-state and a distribution of emitting on-states with different intensities. All the experimentally observed photo-induced effects could be accounted for by introducing a characteristic lifetime tPI of the on-state in the simulations. The QDs on glass presented a tPI proportional to P-1 suggesting the presence of a one-photon process. Light scattering images and spectra of colloidal and C-shaped gold nano-particles were acquired. The minimum size of a metallic scatterer detectable with the SCOM lies around 20 nm.

Raman amplification and performance altering effects

This thesis presents an experimental investigation into several applications of the Raman scattering effect in communication optical fibres as well as how some of these applications can be modified to enhance the resulting performance. The majority of the work contained within is based on laboratory results using many commercially available components. The results can be divided into and presented in three main parts: Firstly, a novel application of a known effect is used to broaden Raman pump light in order to achieve a more continuous distribution of gain with respect to wavelength. Multiple experimental results are presented, all based around the prior spreading of the pump spectrum before being used in the desired transmission fibre. Gathered results show that a notable improvement can be obtained from applying such a technique along with the scope for further optimisation work. Secondly, an investigation into the interaction between the well known effect of Four Wave Mixing (FWM) and Raman scattering is provided. The work provides an introduction to the effect as well commenting on previous literature regarding the effect and its mitigation. In response to existing research experimental results are provided detailing some limitations of proposed schemes along with concepts of how further alleviation from the deleterious effects maybe obtained. Lastly, the distributed nature of the Raman gain process is explored. A novel technique on how a near constant distribution of gain can be employed is implemented practically. The application of distributed gain is then applied to the generation of optical pulses with special mathematical properties within a laboratory setting and finally the effect of pump noise upon distributed gain techniques is acknowledged.

Random distributed feedback Raman fiber laser operating in a 1.2 μm wavelength range

The random distributed feedback fiber laser operating via the stimulated Raman scattering and random distributed feedback based on the Rayleigh scattering is demonstrated in the 1.2 μm frequency band. The RDFB fiber laser generates at 1174 nm up to 2.4 W of output power with corresponding slope efficiency more than 30%. The output radiation has the spectral shape similar to the conventional Raman fiber lasers and spectral width less than 1.7 nm. © 2011 Pleiades Publishing, Ltd.

On two-wavelength Raman fibre laser based on spectral broadening

Raman fibre lasers and converters using the stimulated Raman scattering (SRS) in optical fibre waveguide are attractive for many applications ranging from telecommunications to bio-medical applications [1]. Multiple-wavelength Raman laser sources emitting at two and more wavelengths have been proposed to increase amplification spectrum of Raman fibre amplifiers and to improve noise characteristics [2,3]. Typically, a single fibre waveguide is used in such devices while multi-wavelength generation is achieved by employing corresponding number of fibre Bragg grating (FBG) pairs forming laser resonator. This approach, being rather practical, however, might not provide a good level of cross coherence between radiation generated at different wavelengths due to difference in FBGs and random phase fluctuations between the two wavelengths. In this work we examine a scheme of two-wavelength Raman fibre laser with high-Q cavity based on spectral intracavity broadening [3]. We demonstrate feasibility of such configuration and perform numerical analysis clarifying laser operation using an amplitude propagation equation model that accounts for all key physical effects in nonlinear fibre: dispersion, Kerr nonlinearity, Raman gain, depletion of the Raman pump wave and fibre losses. The key idea behind this scheme is to take advantage of the spectral broadening that occurs in optical fibre at high powers. The effect of spectral broadening leads to effective decrease of the FBGs reflectivity and enables generation of two waves in one-stage Raman laser. The output spectrum in the considered high-Q cavity scheme corresponds to two peaks with 0.2 - 1 nm distance between them. © 2011 IEEE.

Raman Converting laser systems (US 8,494,012 B2)

Preprint

Photochemical dynamics of laser-irradiated semiconductor nanostructures

Thesis (Ph.D.)--University of Washington, 2016-08

Comparison of adhesion layers of gold on silicate glasses for SERS detection

Gold is one of the most widely used metals for building up plasmonic devices. Although slightly less efficient than silver for producing sharp resonance, its chemical properties make it one of the best choices for designing sensors. Sticking gold on a silicate glass substrate requires an adhesion layer, whose effect has to be taken into account. Traditionally, metals (Cr or Ti) or dielectric materials (TiO2 or Cr2O3 ) are deposited between the glass and the nanoparticle. Recently, indium tin oxide and (3-mercaptopropyl)trimethoxysilane (MPTMS) were used as a new adhesion layer. The aim of this work is to compare these six adhesion layers for surface- enhanced Raman scattering sensors by numerical modeling. The near-field and the far-field optical responses of gold nanocylinders on the different adhesion layers are then calculated. It is shown that MPTMS leads to the highest field enhancement, slightly larger than other dielectric materials. We attributed this effect to the lower refractive index of MPTMS compared with the others.

Reduced graphene oxide and Ag wrapped TiO2 photocatalyst for enhanced visible light photocatalysis

A well-organised reduced graphene oxide (RGO) and silver (Ag) wrapped TiO2 nano-hybrid was successfully achieved through a facile and easy route. The inherent characteristics of the synthesized RGO-Ag/TiO2 were revealed through crystalline phase, morphology, chemical composition, Raman scattering, UV-visible absorption, and photoluminescence analyses. The adopted synthesis route significantly controlled the uniform formation of silver nanoparticles and contributed for the absorption of light in the visible spectrum through localized surface plasmon resonance effects. The wrapped RGO nanosheets triggered the electron mobility and promoted visible light shift towards red spectrum. The accomplishment of synergised effect of RGO and Ag well degraded Bisphenol A under visible light irradiation with a removal efficiency of 61.9%.

Amplification d’impulsions brèves de haute énergie par effet Raman stimulé dans les fibres optiques

Le développement au cours des dernières décennies de lasers à fibre à verrouillage de modes permet aujourd’hui d’avoir accès à des sources fiables d’impulsions femtosecondes qui sont utilisées autant dans les laboratoires de recherche que pour des applications commerciales. Grâce à leur large bande passante ainsi qu’à leur excellente dissipation de chaleur, les fibres dopées avec des ions de terres rares ont permis l’amplification et la génération d’impulsions brèves de haute énergie avec une forte cadence. Cependant, les effets non linéaires causés par la faible taille du faisceau dans la fibre ainsi que la saturation de l’inversion de population du milieu compliquent l’utilisation d’amplificateurs fibrés pour l’obtention d’impulsions brèves dont l’énergie dépasse le millijoule. Diverses stratégies comme l’étirement des impulsions à des durées de l’ordre de la nanoseconde, l’utilisation de fibres à cristaux photoniques ayant un coeur plus large et l’amplification en parallèle ont permis de contourner ces limitations pour obtenir des impulsions de quelques millijoules ayant une durée inférieure à la picoseconde. Ce mémoire de maîtrise présente une nouvelle approche pour l’amplification d’impulsions brèves utilisant la diffusion Raman des verres de silice comme milieu de gain. Il est connu que cet effet non linéaire permet l’amplification avec une large bande passante et ce dernier est d’ailleurs couramment utilisé aujourd’hui dans les réseaux de télécommunications par fibre optique. Puisque l’adaptation des schémas d’amplification Raman existants aux impulsions brèves de haute énergie n’est pas directe, on propose plutôt un schéma consistant à transférer l’énergie d’une impulsion pompe quasi monochromatique à une impulsion signal brève étirée avec une dérive en fréquence. Afin d’évaluer le potentiel du gain Raman pour l’amplification d’impulsions brèves, ce mémoire présente un modèle analytique permettant de prédire les caractéristiques de l’impulsion amplifiée selon celles de la pompe et le milieu dans lequel elles se propagent. On trouve alors que la bande passante élevée du gain Raman des verres de silice ainsi que sa saturation inhomogène permettent l’amplification d’impulsions signal à une énergie comparable à celle de la pompe tout en conservant une largeur spectrale élevée supportant la compression à des durées très brèves. Quelques variantes du schéma d’amplification sont proposées, et leur potentiel est évalué par l’utilisation du modèle analytique ou de simulations numériques. On prédit analytiquement et numériquement l’amplification Raman d’impulsions à des énergies de quelques millijoules, dont la durée est inférieure à 150 fs et dont la puissance crête avoisine 20 GW.

Synthesis and characterisation of hybrid gold/polymer nanoparticles for bioassay application

A bioassay technique, based on surface-enhanced Raman scattering (SERS) tagged gold nanoparticles encapsulated with a biotin functionalised polymer, has been demonstrated through the spectroscopic detection of a streptavidin binding event. A methodical series of steps preceded these results: synthesis of nanoparticles which were found to give a reproducible SERS signal; design and synthesis of polymers with RAFT-functional end groups able to encapsulate the gold nanoparticle. The polymer also enabled the attachment of a biotin molecule functionalised so that it could be attached to the hybrid nanoparticle through a modular process. Finally, the demonstrations of a positive bioassay for this model construct using streptavidin/biotin binding. The synthesis of silver and gold nanoparticles was performed by using tri-sodium citrate as the reducing agent. The shape of the silver nanoparticles was quite difficult to control. Gold nanoparticles were able to be prepared in more regular shapes (spherical) and therefore gave a more consistent and reproducible SERS signal. The synthesis of gold nanoparticles with a diameter of 30 nm was the most reproducible and these were also stable over the longest periods of time. From the SERS results the optimal size of gold nanoparticles was found to be approximately 30 nm. Obtaining a consistent SERS signal with nanoparticles smaller than this was particularly difficult. Nanoparticles more than 50 nm in diameter were too large to remain suspended for longer than a day or two and formed a precipitate, rendering the solutions useless for our desired application. Gold nanoparticles dispersed in water were able to be stabilised by the addition of as-synthesised polymers dissolved in a water miscible solvent. Polymer stabilised AuNPs could not be formed from polymers synthesised by conventional free radical polymerization, i.e. polymers that did not possess a sulphur containing end-group. This indicated that the sulphur-containing functionality present within the polymers was essential for the self assembly process to occur. Polymer stabilization of the gold colloid was evidenced by a range of techniques including, visible spectroscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis and Raman spectroscopy. After treatment of the hybrid nanoparticles with a series of SERS tags, focussing on 2-quinolinethiol the SERS signals were found to have comparable signal intensity to the citrate stabilised gold nanoparticles. This finding illustrates that the stabilization process does not interfere with the ability of gold nanoparticles to act as substrates for the SERS effect. Incorporation of a biotin moiety into the hybrid nanoparticles was achieved through a =click‘ reaction between an alkyne-functionalised polymer and an azido-functionalised biotin analogue. This functionalized biotin was prepared through a 4-step synthesis from biotin. Upon exposure of the surface-bound streptavidin to biotin-functionalised polymer hybrid gold nanoparticles, then washing, a SERS signal was obtained from the 2-quinolinethiol which was attached to the gold nanoparticles (positive assay). After exposure to functionalised polymer hybrid gold nanoparticles without biotin present then washing a SERS signal was not obtained as the nanoparticles did not bind to the streptavidin (negative assay). These results illustrate the applicability of the use of SERS active functional-polymer encapsulated gold nanoparticles for bioassay application.

Self-assembled hyperbranched polymer - gold nanoparticle hybrids : understanding the effect of polymer coverage on assembly size and SERS performance

In the past few years, remarkable progress has been made in unveiling novel and unique optical properties of strongly coupled plasmonic nanostructures. However, application of such plasmonic nanostructures in biomedicine remains challenging due to the lack of facile and robust assembly methods for producing stable nanostructures. Previous attempts to achieve plasmonic nano-assemblies using molecular ligands were limited due to the lack of flexibility that could be exercised in forming them. Here, we report the utilization of tailor-made hyperbranched polymers (HBP) as linkers to assemble gold nanoparticles (NPs) into nano-assemblies. The ease and flexibility in tuning the particle size and number of branch ends of a HBP makes it an ideal candidate as a linker, as opposed to DNA, small organic molecules and linear or dendrimeric polymers. We report a strong correlation of polymer (HBP) concentration with the size of the hybrid nano-assemblies and “hot-spot” density. We have shown that such solutions of stable HBP-gold nano-assemblies can be barcoded with various Raman tags to provide improved surface-enhanced Raman scattering (SERS) compared with non-aggregated NP systems. These Raman barcoded hybrid nano-assemblies, with further optimization of NP shape, size and “hot-spot” density, may find application as diagnostic tools in nanomedicine.

Honeycomb nanogold networks with highly active sites

The formation of macroporous honeycomb gold using an electrochemically generated hydrogen bubble template is described. The synthesis procedure induces the formation of highly active surfaces with enhanced electrocatalytic and surface enhanced Raman scattering properties.

Hyperbranched polymer-gold nanoparticle assemblies : role of polymer architecture in hybrid assembly formation and SERS activity

Plasmonic gold nano-assemblies that self-assemble with the aid of linking molecules or polymers have the potential to yield controlled hierarchies of morphologies and consequently result in materials with tailored optical (e.g. localized surface plasmon resonances (LSPR)) and spectroscopic properties (e.g. surface enhanced Raman scattering (SERS)). Molecular linkers that are structurally well-defined are promising for forming hybrid nano-assemblies which are stable in aqueous solution and are increasingly finding application in nanomedicine. Despite much ongoing research in this field, the precise role of molecular linkers in governing the morphology and properties of the hybrid nano-assemblies remains unclear. Previously we have demonstrated that branched linkers, such as hyperbranched polymers, with specific anchoring end groups can be successfully employed to form assemblies of gold NPs demonstrating near-infrared SPRs and intense SERS scattering. We herein introduce a tailored polymer as a versatile molecular linker, capable of manipulating nano-assembly morphologies and hot-spot density. In addition, this report explores the role of the polymeric linker architecture, specifically the degree of branching of the tailored polymer in determining the formation, morphology and properties of the hybrid nano-assemblies. The degree of branching of the linker polymer, in addition to the concentration and number of anchoring groups, is observed to strongly influence the self-assembly process. The assembly morphology shifts primarily from 1D-like chains to 2D plates and finally to 3D-like globular structures, with increase in degree of branching. Insights have been gained into how the morphology influences the SERS performance of these nano-assemblies with respect to hot-spot density. These findings supplement the understanding of the morphology determining nano-assembly formation and pave the way for the possible application of these nano-assemblies as SERS bio-sensors for medical diagnostics.